Patent GB-586999-A (GB)
Title: New vat dyes of the phthaloylacridone series
Filed: 1944-08-15
Abstract: 31 : 41-Phthaloylacridones of the formula <FORM:0586999/IV/1> are prepared by bringing about ring closure in known manner in a compound and, where Z is not already an aroylamino group, converting it thereto by known means <FORM:0586999/IV/2> where X is an alkanesulphonyl radical, Y is hydrogen halogen or a sulphonic acid group, R is an aryl radical, Z is an aroylamino group or an amino group or a halogen atom, and A is hydrogen or alkyl.  The preferred method of ring closure is by means of chlorosulphonic acid, but treatment with an alkaline solution of sodium hydrosulphite may be used.  In those cases where Y is halogen or a sulphonic acid group, it is advantageous to replace it by hydrogen.  In the case where Y is halogen, this is preferably done by the method described in Specification 587,006. The phenyl radical may be substituted by such substituents as alkane, aralkane, or benzene sulphonyl.  Starting materials mentioned include 2-bromo-1-amino - 4 - (41 - methanesulphonyl - 21 - carboxy - anilino) - anthraquinone 2, - bromo - 1 - amino - 4 - (21 - carboxy - 51 - n - butanesulphonylanilino) - anthraquinone 1 - amino - 4 - (21 - carboxy - 51 - methane - sulphonylanilino - anthraquinone 1 - benzoylamino-4-(21-carbomethoxy-41-methane sulphonylanilino) anthraquinone, 1 - benzoylamino - 4 - (21 - carbomethoxy - 61 - methanesulphonylanilino) anthraquinone, 4 - chloro - 1 - (21-carboxy - 51 - methanesulphonylanilino) anthraquinone 2-bromo-1-amino-4-(21-carboxy-51 -methanesulphonylanilino) anthraquinone, 2-bromo-1-amino-4-(21-carboxy-51-methanesul phonylanilino) anthraquinone and 1-amino-4-(41 - methanesulphonyl - 21 - carboxyanilino) anthraquinone-2-sulphonic acid.  In examples: (1) 2-Bromo-1-amino-4-(41-methanesulphonyl-21 -carboxyanilino) anthraquinone is added to chlorosulphonic acid at 15-20 DEG  C. and the solution so obtained poured into an excess of cold water and the product filtered to give 7-bromo-6-amino-10-methanesulphonyl-31 : 41-phthaloylacridone which dissolves in caustic soda solution on the addition of sodium hydrosulphite solution to give a purple-brown vat. The 7-bromine atom may be removed as described in Specification 587,006 to give 6-amino-10-methanesulphonyl-31 : 41-phthaloylacridone which dyes cotton bright blue from a purple vat.  This dye may be acylated with benzoyl chloride in nitrobenzene to give the 6-benzoylamino compound.  Other acylating agents are anisyl chloride, p-toluyl chloride m-chlorobenzoyl chloride p - methanesulphonylbenzoyl chloride and p - phenylmethanesulphonylbenzoyl chloride.  (2) 2-Bromo-1-amino-4 - (21 - carboxy - 51 - methanesulphonylanilino) anthraquinone is treated as in example (1) to give 6 - amino - 11 - methanesulphonyl - 31 : 41 - phthaloylacridone. This compound is then treated with the aroylating agents referred to in example (1) to give the corresponding aroylamino compounds. Additional aroylating agents mentioned are p-n-butanesulphonyl chloride, diphenyl sulphone-4-carboxylic acid chloride, and p-(2 : 6-dichlorophenyl) methanesulphonylbenzoyl chloride.  (3) 2-Bromo-1-amino - 4 - (21 - carboxy - 31 - methanesulphonylanilino) anthraquinone is treated as in example (1) to give 6-amino-9-methanesulphonyl-31 : 41-phthaloylacridone which is then treated with aroylating agents as in example (1).  (4) 2-Bromo-1-amino-4-(21-carboxy-51-n-butanesul phonylanilino) anthraquinone is treated as in example (1) to give 6-amino-11-n-butanesulphonyl-31 : 41-phthaloylacridone which is then treated with aroylating agents as described in example (1).  (5) 1-Bromo-4-(21-carboxy-51-methanesulphonylanilino) anthraquinone is treated as in example (1) to give the same phthaloylacridone as prepared in example (2).  (6) 1 - Benzoylamino - 4 - (21-carbomethoxy-41-methanesulphonylanilino) anthraquinone is made into a paste with ethanol and there is then added an aqueous alkaline solution of sodium hydrosulphite.  A current of air is then blown through the solution to form the same phthaloylacridone as is formed in example (1).  (7) 1 - Benzoylamino - 4 - (21-carbomethoxy-61-methanesulphonylanilino) anthraquinone is treated as in example (6).  (8) 1-Amino-4-(21-carboxy-41-methanesulphonylanilino) anthraquinone is treated as in example (1) to give the same product as is obtained in example (1).  (9) 4 - Chloro - 1 - (21 - carboxy - 51 - methanesulphonylanilino) anthraquinone is treated as in example (1) to form 6-chloro-11-methanesulphonyl-31 : 41-phthaloylacridone which is converted to the 6-amino compound by treatment with p - toluene - sulphonamide, potassium acetate, copper acetate and nitrobenzene. The starting materials for this invention are made by the condensation of a substituted or unsubstituted 1 - amino - 4 - halogeno - anthraquinone with an o-aminobenzene carboxylic acid carrying in appropriate position an alkane-sulphonyl radical. 2-Bromo-1-amino-4-(p-methanesulphonyl-o-carboxyanilino) anthraquinone is described in example (1) as being made by heating 2 : 4-dibromo - 1 - amino - anthraquinone with 5 - methanesulphonylanthranilic acid in phenol with potassium acetate cuprous chloride and potassium carbonate.  5 - Methane - sulphonylanthranilic acid is prepared by the diazotization of 6-nitro-3-aminobenzoic acid treatment of the diazonium salt with potassium ethyl xanthate and dimethyl sulphate and oxidation of the 6-nitro-3-methylmercaptobenzoic acid followed by reduction.  2-Bromo-1-amino-4-(21-carboxy-51-methane sulphonylanilino) anthraquinone is prepared by heating 2 : 4 - dibromo - 1 - amino - anthraquinone with 4-methanesulphonylanthranile acid as in example (1).  4 - Methanesulphonylanthranilic acid is prepared by nitration of methyl-p-tolyl sulphone to methyl - 2 - nitro - 4 - methylphenyl sulphone, oxidation of this to 2-nitro-4-methane-sulphonylbenzoic acid and reduction by ferrous sulphate in ammonia.  2-Bromo-1-amino-4-(21-carboxy-31-methane sulphonylanilino) anthraquinone is made by condensation of 2 : 4-dibromo-1-amino anthraquinone with 6-methanesulphonylanthranilic acid as in example (1).  6-Methanesulphonylanthranilic acid is made by diazotization of 6-nitroanthranilic acid and further treatment as for the 5-methane-compound above. 2-Bromo-1-amino-4-(21-carboxy-51-n-butane sulphonylanilino) anthraquinone is made by heating 2 : 4-dibromo-1-amino-anthraquinone with 4-n-butanesulphonyl-anthranilic acid as in example (1). 4-n-Butanesulphonylanthranilic acid is made by a process similar to the 4-methane-compound above from n-butyl-p-tolylsulphone. 1-Amino-4-(21-carboxy-31-methanesulphonylanilino) anthraquinone is made from the corresponding 2-sulphonic acid by treatment with glucose.  The parent 2-sulphonic acid is itself made by treating 1-amino-4-bromo-anthraquinone-2-sulphonic acid with 4-methanesulphonylanthranilic acid as in example (1). p  1 - Benzoylamino - 4 - (21 - carbomethoxy - 41 - methanesulphonylanilino) anthraquinone is made heating 1 - amino - 4 - benzoylamino - anthraquinone with methyl 5-methanesulphonyl-2-chlorobenzoate as in example (1).  The 61-methanesulphonylanilino compound is similarly made.  Methyl - 5 - methanesulphonyl - 2 - chlorobenzoate is made by the Sandmeyer reaction from 5-methanesulphonyl anthranilic acid, and esterification with methyl alcohol. 1-Amino-4-(21-carboxy-41-methanesulphonylaniliono) anthraquinone is made by heating 5-methanesulphonyl-2-chlorobenzoic acid with 1 : 4-diamino-anthraquinone as in example (1). 4-Chloro-1-(21-carboxy-51-methanesulphonylanilino) anthraquinone is made by heating 4-methanesulphonylanthranilic acid with 1 : 4-dichloro-anthraquinone as in example (1).